CN113797957B - Catalyst with mesoporous molecular sieve as carrier and preparation method and application thereof - Google Patents

Catalyst with mesoporous molecular sieve as carrier and preparation method and application thereof Download PDF

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CN113797957B
CN113797957B CN202010550916.XA CN202010550916A CN113797957B CN 113797957 B CN113797957 B CN 113797957B CN 202010550916 A CN202010550916 A CN 202010550916A CN 113797957 B CN113797957 B CN 113797957B
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molecular sieve
mesoporous molecular
carrier
catalyst
precursor
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CN113797957A (en
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武洁花
赵清锐
邵芸
张明森
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/08—Heat treatment
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    • B01J37/088—Decomposition of a metal salt
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C07—ORGANIC CHEMISTRY
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract

The invention relates to the field of catalysis, and discloses a catalyst taking a mesoporous molecular sieve as a carrier, and a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component loaded on the carrier, and the carrier is the mesoporous molecular sieve; the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20; wherein the average pore diameter of the carrier is 5-10nm. The catalyst has larger pore diameter and more active sites for loading active components, and meanwhile, the larger pore diameter is more beneficial to the diffusion of reactants and products.

Description

Catalyst with mesoporous molecular sieve as carrier and preparation method and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to a catalyst taking a mesoporous molecular sieve as a carrier, and a preparation method and application thereof.
Background
Ethylene is the largest fundamental component of commodity chemicals and chemicals in the world. Ethylene and other c2+ hydrocarbon products may also be produced from methane by Oxidative Coupling (OCM) reactions of methane. The technology is used for reducing ethylene (C 2 H 4 ) The method has great potential in the aspects of cost, energy and environmental emission in production, and meanwhile, because the methane oxidative coupling reaction is a strong exothermic reaction and is carried out at high temperature and is limited by the reaction temperature and the technical difficulty of the reaction process, no industrial-scale production is yet developed so far, and therefore, the development of the methane oxidative coupling catalyst with excellent performance has practical significance.
In order to reduce the reaction temperature of methane oxidative coupling catalysts, researchers have done much work, such as CN109922880A discloses a methane Oxidative Coupling (OCM) catalyst composition characterized by the general formula Sr 1.0 Ce a Yb b O c Wherein a is about 0.01 to about 2.0, wherein b is about 0.01 to about 2.0, wherein the sum (a+b) is not 1.0, and wherein c balances the oxidation state. CN109890501a discloses a methane Oxidative Coupling (OCM) catalyst composition comprising: (i) Sr-Ce-Yb-O perovskite; (ii) One or more metal oxides selected from the group consisting of strontium (Sr), cerium (Ce) and ytterbium (Yb); wherein the one or more oxides comprise: single metal oxide, single metal oxide mixture, mixed goldThe metal oxide is an oxide, a mixture of mixed metal oxides, a mixture of a single metal oxide and a mixed metal oxide, or a combination thereof. The prepared catalyst has the problems of high reaction temperature, complex catalyst preparation process and long preparation period, and brings difficulty to industrial scale-up production.
Disclosure of Invention
The invention aims to solve the problems of high reaction temperature, complex catalyst preparation process and poor reaction stability in the prior art, and provides a catalyst taking a mesoporous molecular sieve as a carrier, a preparation method and application thereof, wherein the catalyst has larger pore diameter and more active sites for loading active components, and meanwhile, the larger pore diameter is more beneficial to the diffusion of reactants and products; when the catalyst taking the mesoporous molecular sieve as a carrier is prepared, a template agent, a silicon source and a pore-expanding agent are added, and under an acidic condition, the preparation of the mesoporous molecular sieve with larger aperture is more facilitated through the synergistic effect of the template agent, the silicon source and the pore-expanding agent, so that the catalyst has more active sites for loading active components; the catalyst can enable the reaction of preparing more than two carbon atoms from methane to be carried out at a lower temperature (such as within the range of 500-750 ℃), reduces the requirements on a reactor and operating conditions, has higher methane conversion rate and higher hydrocarbon selectivity more than two carbon atoms, and is more beneficial to industrialized scale-up production.
In order to achieve the above object, a first aspect of the present invention provides a catalyst using a mesoporous molecular sieve as a carrier, the catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is a mesoporous molecular sieve; the active components comprise La, ba and Li;
wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20;
wherein the average pore diameter of the carrier is 5-10nm.
The catalyst taking the mesoporous molecular sieve as the carrier has larger pore diameter and more active sites for loading active components, and meanwhile, the larger pore diameter is more beneficial to the diffusion of reactants and products, so that the oxidation coupling reaction of methane is promoted.
In a second aspect of the present invention, there is provided a method of preparing a mesoporous molecular sieve supported catalyst, the method comprising:
(1) Under an acidic condition, carrying out contact reaction on a template agent, a pore-expanding agent, water and a silicon source, and then sequentially carrying out solid-liquid separation and roasting to obtain a mesoporous molecular sieve;
(2) Loading active components on a mesoporous molecular sieve, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20.
In a third aspect of the present invention, a catalyst using a mesoporous molecular sieve as a carrier is provided, and the catalyst using the mesoporous molecular sieve as the carrier is prepared by the above method.
In a fourth aspect of the invention, there is provided a process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the catalyst taking the mesoporous molecular sieve as a carrier in the presence of oxygen;
or preparing a catalyst taking the mesoporous molecular sieve as a carrier according to the method, and then contacting methane with the catalyst taking the mesoporous molecular sieve as the carrier in the presence of oxygen.
According to the method for preparing the catalyst taking the mesoporous molecular sieve as the carrier, the pore-expanding agent is added into the reaction system in the process of preparing the mesoporous molecular sieve, and the mesoporous molecular sieve with larger pore diameter is prepared more favorably through the synergistic effect of the template agent, the silicon source and the pore-expanding agent, so that the catalyst has more active sites for loading active components, and the oxidation coupling reaction of methane is promoted.
The method for preparing the hydrocarbon with more than two carbon atoms from the methane provided by the invention is characterized in that the methane is contacted with the catalyst taking the mesoporous molecular sieve as a carrier in the presence of oxygen to prepare the hydrocarbon with more than two carbon atoms, and the catalyst taking the mesoporous molecular sieve as the carrier can enable the reaction for preparing the hydrocarbon with more than two carbon atoms from the methane to be carried out at a lower temperature (such as a range of 500-650 ℃), thereby reducing the requirements on a reactor and operating conditions, having higher methane conversion rate and higher hydrocarbon selectivity with more than two carbon atoms, and being more beneficial to industrialized large-scale production.
Drawings
Fig. 1 is a transmission electron microscope TEM image of a mesoporous molecular sieve obtained according to example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalyst taking a mesoporous molecular sieve as a carrier, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is the mesoporous molecular sieve; the active components comprise La, ba and Li;
wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20;
wherein the average pore diameter of the carrier is 5-10nm.
In some embodiments of the invention, preferably, the molar ratio of La, ba and Li is 1:0.005-0.007:1.6-16.
In some embodiments of the invention, the specific surface area, pore volume and pore diameter of the catalyst may be measured according to a nitrogen adsorption method, the specific surface area is calculated using a BET method, and the pore volume is calculated using a BJH model. The specific surface area of the support is preferably 700 to 1000m 2 Preferably 750-900m 2 And/g. The pore volume of the support is preferably from 0.5 to 2.5cm 3 Preferably 0.6-2cm 3 And/g. The average pore diameter of the support is preferably 8 to 10nm.
In some embodiments of the present invention, the carrier is preferably present in an amount of 64 to 96.89 wt%, more preferably 72 to 94.89 wt%, based on the total weight of the catalyst, in order to further secure the catalytic effect of the catalyst. The La content is preferably 3 to 15% by weight, more preferably 5 to 12.5% by weight. The content of Ba is preferably 0.01 to 2% by weight, more preferably 0.4 to 0.4% by weight. The content of Li is preferably 0.01 to 15% by weight, more preferably 0.5 to 10% by weight.
In some embodiments of the invention, the active component is present in an oxidized form.
In a second aspect of the present invention, there is provided a method of preparing a mesoporous molecular sieve supported catalyst, the method comprising:
(1) Under an acidic condition, carrying out contact reaction on a template agent, a pore-expanding agent, water and a silicon source, and then sequentially carrying out solid-liquid separation and roasting to obtain a mesoporous molecular sieve;
(2) Loading active components on a mesoporous molecular sieve, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20.
In some embodiments of the invention, the mesoporous molecular sieve has an XRD pattern with characteristic peaks at 100 DEG+ -0.3 DEG, 110 DEG+ -0.3 DEG and 200 DEG+ -0.3 DEG of 2 theta.
In some embodiments of the present invention, the pore-expanding agent is a substance capable of making the pore diameter of the mesoporous molecular sieve larger, and the pore-expanding agent is preferably at least one selected from polystyrene and mesitylene; more preferably polystyrene nanomicrospheres.
In some embodiments of the invention, the polystyrene nanospheres have an average diameter of less than 200nm.
In some embodiments of the invention, the polystyrene nanoparticle may be prepared by itself. According to a preferred embodiment of the present invention, the preparation method of the polystyrene nanoparticle comprises the following steps: in the presence of a solvent, mixing styrene and an initiator for polymerization reaction, and then carrying out solid-liquid separation to obtain the polystyrene nano microsphere.
In some embodiments of the invention, preferably, the solvent is water, more preferably nitrogen deaerated water.
In some embodiments of the present invention, the method of preparing polystyrene nanomicrospheres may further comprise washing the styrene with an alkaline solution, followed by washing with water (preferably deionized water) to remove the polymerization inhibitor from the styrene feedstock.
In some embodiments of the invention, preferably, the alkaline substance in the alkaline liquor is at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate and potassium hydroxide, preferably sodium hydroxide. Preferably, the molar concentration of the alkaline substance is 0.05-0.1mol/L.
In some embodiments of the present invention, the method of preparing polystyrene may further include crushing and grinding the polystyrene to obtain polystyrene powder.
In some embodiments of the invention, the initiator is preferably at least one of persulfate, sulfate, and sulfite; more preferably, the initiator is a persulfate.
In some embodiments of the invention, the persulfate salt is a water-soluble salt, preferably sodium persulfate and/or potassium persulfate.
In some embodiments of the invention, preferably, the initiator, the styrene and the solvent are used in amounts such that the molar ratio of the initiator, the styrene and the solvent is from 1:50 to 100:3000-4000. In the process of preparing the pore-expanding agent, the solvent may be water.
In some embodiments of the present invention, to further highly order the structure of the pore-expanding agent, it is preferred that the polymerization reaction is carried out under stirring at a rotational speed of 400 to 500 rpm.
In some embodiments of the invention, to separate the reamer from the solution as quickly as possible, it is preferred to centrifuge with a centrifuge at a speed of 6000 to 8000 rpm to recover the solid product.
In some embodiments of the invention, the polymerization reaction temperature is preferably 70-80 ℃ to further promote the formation of the pore-expanding agent. The polymerization time is preferably 18 to 24 hours.
In some embodiments of the invention, to further promote the formation of the pore-expanding agent, the mixing is performed by adding the initiator to styrene at a rate of 0.1-10g/min based on 1g of styrene, and after the addition is completed, the resulting mixed solution is allowed to stand for 20-22 hours.
In some embodiments of the invention, in step (1), the pH of the acidic conditions is controlled to 2-5 using an acidic substance; the acidic substance is at least one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.
In some embodiments of the present invention, the template agent may be a nonionic surfactant, which is mainly synthesized in a special structure, and plays a role in structure guiding; preferably having the general formula EO a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a); more preferably, wherein a has a value of 10 to 100 and b has a value of 40 to 80; further preferred is EO 20 PO 70 EO 20 And/or EO 17 PO 55 EO 17 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, the source of the templating agent is not limited in the present invention and can be obtained commercially (for example, from Sigma-Aldrich under the trade name P123, molecular formula EO 20 PO 70 EO 20 ) Can also be prepared by adopting a method in the prior art, and is not repeated here.
In some embodiments of the present invention, the kind of the silicon source is not particularly limited as long as the silicon element can be provided, and preferably, the silicon source is sodium silicate and/or tetramethyloxysilane, more preferably, tetraethyl silicate.
In some embodiments of the invention, preferably, the molar ratio of La, ba and Li is 1:0.005-0.007:1.6-16.
In some embodiments of the invention, to further ensure the formation of mesoporous molecular sieves, in step (1), the template, the water and the silicon source in Si are used in amounts such that the molar ratio of the template, the water and the silicon source in Si is 1:30000-65000:40-60;
in some embodiments of the invention, in order to further increase the pore size of the catalyst, in step (1), the pore expanding agent and the templating agent are used in such an amount that the mass ratio of the pore expanding agent to the templating agent is 3-5:1.
In the invention, the adding sequence and the adding conditions of the template agent, the silicon source, the water and the pore-expanding agent are not limited, preferably, the template agent, the silicon source and the water are contacted at the stirring rotation speed of 700-900 rpm, the mixture obtained after the contact and the pore-expanding agent are mixed and reacted at the stirring rotation speed of 90-150 rpm, and then the mixture is condensed and baked in sequence to obtain the mesoporous molecular sieve.
In the invention, in order to accelerate the dissolution of the template agent, in the step (1), the contact system can be subjected to ultrasonic treatment, wherein the ultrasonic treatment temperature can be 30-50 ℃ and the ultrasonic treatment time can be 3-5h.
In some embodiments of the invention, to further promote the formation of mesoporous molecular sieves, in step (1), the contacting reaction is performed in a manner that: the addition of the silicon source to the templating agent is carried out at a rate of 0.1 to 10g/min, preferably 0.1 to 5g/min, based on 1g of templating agent.
In some embodiments of the invention, in order to shorten the reaction time, in step (1), the contact reaction is carried out under vacuum conditions, preferably a vacuum of 80-100 mbar; the temperature of the contact reaction is preferably 40-50 ℃ and the time is preferably 2-4h.
In some embodiments of the invention, in step (1), the temperature of the firing is preferably 500-600 ℃; the calcination time is preferably 0.5 to 10 hours, more preferably 3 to 9 hours.
In some embodiments of the present invention, in step (2), there is no limitation on the manner of loading, and conventional technical means in the prior art may be adopted, preferably, the manner of loading is: and impregnating the mesoporous molecular sieve with impregnating solution containing lanthanum precursor, barium precursor and lithium precursor, and then sequentially drying and roasting to obtain the catalyst taking the mesoporous molecular sieve as a carrier. Specifically, the capillary pressure of the pore channel structure of the carrier is relied on to enable the metal component to enter the pore channel of the mesoporous structure, and meanwhile, the metal component is adsorbed on the surface of the mesoporous molecular sieve until the metal component reaches adsorption equilibrium in the carrier. The impregnation may be co-impregnation or may be a stepwise impregnation, preferably co-impregnation.
In some embodiments of the present invention, in step (2), the concentration of the lanthanum precursor in terms of lanthanum element is preferably 0.01 to 0.5 wt% and the concentration of the barium precursor in terms of barium element is preferably 0.001 to 0.3 wt% and the concentration of the lithium precursor in terms of lithium element is preferably 0.0001 to 0.1 wt% in the impregnation liquid.
In some embodiments of the invention, in step (2), the impregnating solution is used in an amount of 80 to 120g per gram of carrier.
In some embodiments of the present invention, there is no particular limitation on the lanthanum precursor, preferably, in step (2), the lanthanum precursor is a water-soluble lanthanum salt, more preferably at least one selected from lanthanum nitrate, lanthanum chloride, and lanthanum chlorate, and further preferably lanthanum nitrate.
In some embodiments of the present invention, there is no particular limitation on the barium precursor, preferably, the barium precursor is a water-soluble barium salt, more preferably selected from barium nitrate and/or barium chloride;
in some embodiments of the present invention, there is no particular limitation on the lithium precursor, preferably, the lithium precursor is a water-soluble lithium salt, more preferably selected from lithium nitrate and/or lithium acetate, and further preferably lithium nitrate.
In some embodiments of the invention, the time of the impregnation in step (2) is preferably 1 to 6 hours, more preferably 1 to 3 hours, in order to allow more sufficient contact of the support with the precursor solution. The temperature of the impregnation is preferably 30-80 ℃.
In the present invention, in the step (2), the treatment process of removing the solvent after the completion of the impregnation may be a conventional method in the art, and for example, a rotary evaporator may be used to remove the solvent in the impregnation system.
In some embodiments of the present invention, in step (2), the drying may be performed using methods conventional in the art, preferably the drying is performed in a drying apparatus, and the drying conditions may include a drying temperature preferably ranging from 100 to 110 ℃. The drying time is preferably 1 to 3 hours.
In some embodiments of the invention, in step (2), the calcination temperature is preferably 500-650 ℃ in order to promote catalyst formation. The calcination time is preferably 4 to 5 hours.
In the present invention, the method may further include a step of using the obtained mesoporous molecular sieve-supported catalyst. The molding method is not limited, and a conventional extrusion molding can be adopted, and the shape of the obtained molded catalyst taking the mesoporous molecular sieve as a carrier can be cylindrical, honeycomb or sheet. And then crushing and screening the formed catalyst taking the mesoporous molecular sieve as a carrier, wherein the particle size of the crushed catalyst taking the mesoporous molecular sieve as the carrier is 40-60 meshes.
In a third aspect of the present invention, a catalyst using a mesoporous molecular sieve as a carrier is provided, and the catalyst using the mesoporous molecular sieve as the carrier is prepared by the above method.
In a fourth aspect of the invention, there is provided a process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the catalyst taking the mesoporous molecular sieve as a carrier in the presence of oxygen;
or preparing a catalyst taking the mesoporous molecular sieve as a carrier according to the method, and then contacting methane with the catalyst taking the mesoporous molecular sieve as the carrier in the presence of oxygen.
In the present invention, the contacting may be performed in a continuous flow reactor, and the present invention is not limited to the type of continuous flow reactor, and may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or an ebullated bed reactor. In particular, the mesoporous molecular sieve supported catalyst may be layered in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullated bed).
In some embodiments of the invention, to facilitate the catalytic reaction, to increase the conversion of methane and to increase the selectivity to hydrocarbons with more than two carbons, the molar ratio of methane to the oxygen may be from 2 to 8:1, preferably 3-8:1.
In the present invention, the conditions of the contact are not particularly limited, and may be selected conventionally in the art, and preferably the contact temperature is 500 to 750 ℃. The time of the contacting may be 1 to 12 hours; the pressure of the contact is 0.005-0.5MPa, the space velocity of methane is 10000-100000 mL/(g.h), and the preferential pressure is 20000-75000 mL/(g.h).
In the present invention, the hydrocarbon having two or more carbon atoms is at least one selected from the group consisting of ethane, ethylene, propane and propylene.
In the present invention, the unit "mL/(g.h)" is the amount of the total gas of methane and oxygen (mL) used for 1 hour with respect to 1g of the catalyst.
In the present invention, the pressures refer to gauge pressure.
The present invention will be described in detail by examples.
In both examples and comparative examples, the reagents used were commercially available analytically pure reagents. Room temperature refers to 25 ℃. The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A. The muffle furnace is available from CARBOLITE company under the model CWF1100. Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer was purchased from Sigma-Aldrich under the trade name P123 and the molecular formula EO 20 PO 70 EO 20 Molecular weight 5800. Tetraethyl silicate, analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd. In the experimental process, the pH value is measured by adopting a Metler pH meter S220, the styrene reagent is purchased from Shanghai Alasdine Biochemical technology Co., ltd, the potassium persulfate is purchased from Beijing chemical reagent Co., the national medicine group, and the alumina molecular sieve is purchased from Henan Mingze environmental protection technology Co.
Preparation example 1
Washing 100mL of styrene with an equal volume of sodium hydroxide solution for six times, wherein the concentration of sodium hydroxide is 0.1mol/L, washing the styrene with an equal volume of distilled water for six times, adding the washed organic phase into 835mL of nitrogen deaerated water at 80 ℃, adding 50mL of potassium persulfate aqueous solution with stirring at 500 revolutions per minute, wherein the concentration of potassium persulfate is 0.24mol/L, the adding speed of potassium persulfate is 0.5mL/min, centrifuging the reaction mixture for 22 hours, separating the reaction mixture for 20 minutes by using a centrifuge, recovering a solid product at 8000 revolutions per minute, and obtaining the pore-expanding agent, wherein the average diameter of the obtained pore-expanding agent polystyrene nano-microsphere is 100nm as shown by SEM analysis and detection.
Example 1
Adding 1g of template agent P123 into a solution (pH value is 4.2) consisting of 25mL of hydrochloric acid with the concentration of 2mol/L and 8g of deionized water, stirring to completely dissolve the P123, carrying out ultrasonic treatment at the temperature of 40 ℃ for 2 hours, adding 2g of tetramethoxysilane (the adding rate of tetramethoxysilane is 0.1 g/min), stirring for 10 minutes at the rotating speed of 850 r/min, adding 3g of pore-expanding agent obtained in preparation example 1, stirring the mixture uniformly at the rotating speed of 120 r/min, heating the mixture at the temperature of 40 ℃ under the vacuum of 100 mbar for 3 hours, transferring to air for condensation at the temperature of room temperature, and roasting at the temperature of 560 ℃ for 4 hours in a muffle furnace to obtain the mesoporous molecular sieve.
0.23g (0.0005 mol) lanthanum nitrate hexahydrate, 0.012g (4.6X10) were weighed out -5 mol) barium nitrate and 0.005g (7.2X10) -5 mol) lithium nitrate is added into 100g deionized water, the mixture is stirred uniformly, 1g mesoporous molecular sieve prepared in preparation example 1 is added into the uniformly mixed solution, the solution is immersed for 6 hours at the temperature of 45 ℃, then water in the system is removed by a rotary evaporator, a solid product is obtained, the solid product is placed into a 110 ℃ oven for drying for 2 hours, then the solid product is placed into a muffle furnace for setting the temperature of 650 ℃, and the catalyst taking the mesoporous molecular sieve as a carrier is obtained after roasting for 5 hours.
Example 2
1g (0.00017 mol) of template P123 is added into a solution (pH value is 3.5) consisting of 25mL of hydrochloric acid with the concentration of 2mol/L and 10g of deionized water, stirring is carried out to dissolve the P123 completely, ultrasonic treatment is carried out at the temperature of 40 ℃ for 2h, 1.67g of tetramethoxysilane (the adding rate of the tetramethoxysilane is 0.3 g/min) is added, stirring is carried out for 6min at the rotating speed of 800 rpm, 4g of the pore expanding agent obtained in the preparation example 1 is added, the mixture is uniformly stirred at the rotating speed of 100 rpm, then the mixture is heated at the temperature of 45 ℃ under the vacuum of 100 mbar for 2h, the mixture is transferred into air for condensation at the room temperature, and roasting is carried out at the temperature of 500 ℃ for 6h in a muffle furnace, thus obtaining the mesoporous molecular sieve.
Weighing 0.32g (0.0007 mol) of lanthanum nitrate hexahydrate, 0.02g (7.65X10) -5 mol) barium nitrate and 0.04g (0.0006 mol) lithium nitrate are added into 100g deionized water, and then are mixed and stirred uniformly, 1g mesoporous molecular sieve prepared in preparation example 1 is added into the uniformly mixed solution, and then is immersed1.5h, the temperature is 50 ℃, then a rotary evaporator is used for removing water in the system to obtain a solid product, the solid product is placed in a baking oven at 100 ℃, dried for 3h, then placed in a muffle furnace, the temperature is set at 550 ℃, and baked for 4h, thus obtaining the catalyst taking the mesoporous molecular sieve as a carrier.
Example 3
1g (0.00017 mol) of template P123 is added into a solution (pH value is 3.8) consisting of 25mL of hydrochloric acid with the concentration of 2mol/L and 12.5g of deionized water, stirring is carried out to dissolve the P123 completely, ultrasonic treatment is carried out at the temperature of 40 ℃ for 4 hours, 1.8g of tetramethoxysilane (the adding rate of the tetramethoxysilane is 0.2 g/min) is added, stirring is carried out at the rotating speed of 750 revolutions per minute for 5 minutes, 3.7g of the pore-expanding agent obtained in preparation example 1 is added, the mixture is uniformly stirred at the rotating speed of 130 revolutions per minute, then the mixture is heated at the temperature of 40 ℃ under the vacuum of 100 mbar for 4 hours, transferred into air for condensation at the room temperature, and baked at the temperature of 600 ℃ for 4 hours in a muffle furnace, thus obtaining the mesoporous molecular sieve.
Weighing 0.48g (0.0011 mol) of lanthanum nitrate hexahydrate, 0.24g (9.2X10) -4 mol) barium nitrate and 0.01g (1.45X10) -4 mol) lithium nitrate is added into 200g deionized water, the mixture is uniformly mixed, 2g mesoporous molecular sieve prepared in preparation example 1 is added into the uniformly mixed solution, the solution is immersed for 3 hours at the temperature of 80 ℃, then solvent water in the system is removed by a rotary evaporator to obtain a solid product, the solid product is placed into a 110 ℃ oven for drying for 2 hours, placed into a muffle furnace for setting the temperature of 650 ℃ and baked for 5 hours, and the catalyst taking the mesoporous molecular sieve as a carrier is obtained.
Comparative example 1
A catalyst supported on a mesoporous molecular sieve was prepared according to the method of example 1, except that an alumina molecular sieve was used instead of the prepared mesoporous molecular sieve.
Comparative example 2
A catalyst supported on a mesoporous molecular sieve was prepared as in example 1, except that a pore-expanding agent was not used.
Comparative example 3
A catalyst supported on a mesoporous molecular sieve was prepared as in example 1, except that lanthanum nitrate was replaced with equimolar cerium nitrate and barium nitrate was replaced with equimolar zinc nitrate.
Comparative example 4
A catalyst supported on a mesoporous molecular sieve was prepared as in example 2, except that lanthanum nitrate, barium nitrate and lithium nitrate were used in amounts such that the molar ratio of La, ba and Li was 0.5:1:1.5.
Test example 1
0.1g of the catalyst with the mesoporous molecular sieve as a carrier obtained in the examples and the comparative example is filled into a fixed bed reactor for preparing more than two hydrocarbons by oxidative coupling of methane, wherein the reaction pressure is 0.008MPa, and the reaction pressure is methane: the molar ratio of oxygen was 6:1, the contact temperature was 650 ℃, the reaction time was 5h, the space velocity of methane was 40000 mL/(g.h), and the reaction product was collected after the reaction.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A. Wherein hydrocarbons such as methane, ethane, ethylene, propane and propylene are detected by an alumina column FID detector, methane, carbon monoxide, carbon dioxide and oxygen are detected by a carbon molecular sieve column TCD detector, and calculated by a carbon balance method.
The calculation method of methane conversion rate and the like is as follows:
methane conversion = amount of methane consumed by the reaction/initial amount of methane x 100%
Ethylene selectivity = amount of methane consumed by ethylene produced/total amount of methane consumed x 100%
Ethane selectivity = amount of methane consumed by ethane produced/total amount of methane consumed x 100%
Propane selectivity = amount of methane consumed by propane produced/total amount of methane consumed x 100%
Propylene selectivity = amount of methane consumed by propylene produced/total amount of methane consumed x 100%
Hydrocarbon selectivity over two carbons = ethane selectivity + ethylene selectivity + propylene selectivity + propane selectivity
The results obtained are shown in Table 1.
Test example 2
The nitrogen adsorption and desorption experiments of the mesoporous molecular sieve samples obtained in the examples and comparative examples were performed on an ASAP2020M+C fully automatic physico-chemical adsorption analyzer manufactured by Micromeritics Co. The samples were vacuum degassed at 350 ℃ for 4 hours prior to measurement. The specific surface area of the sample was calculated by the BET method, and the pore volume and average pore diameter were calculated by the BJH model, and the results are shown in Table 1.
Test example 3
The elemental analysis method of the mesoporous molecular sieve supported catalyst in examples and comparative examples was X-ray fluorescence spectroscopy (XRF) analysis, the instrument model of XRF was Malvern pananalytic Epsilon1, and the test results are shown in Table 1, wherein the lanthanum content, barium content and lithium content are shown in Table 1 on the basis of 100wt%, and the balance thereof is the support content.
Test example 4
The mesoporous molecular sieve samples obtained in the examples were tested by X-ray powder diffractometer using a copper target on Bruker D8 addition diffractometer, the characteristic spectrum wavelength of the copper target From XRD patterns, characteristic peaks of the mesoporous molecular sieve at 2 theta angles of 100 degrees, 110 degrees and 200 degrees can be seen, which illustrate that the mesoporous molecular sieve has the basic characteristics of SBA-15. Similarly, the mesoporous molecular sieves obtained in examples 2 and 3 also exhibited characteristic peaks at 2θ angles of 100 °, 110 ° and 200 ° as measured by XRD.
Test example 5
Transmission electron microscopy was performed on the mesoporous molecular sieves obtained in examples and comparative examples, and TEM imaging was performed using JEOL for 2100F FEG TEM with schottky field emission source. Acceleration voltage 200kv, energy dispersive X-ray (EDX) analysis using low background double inclined support and INCAX-Sight silicon (lithium) detector for EDX, area 50mm at 25 ° 2 130eV. The transmission electron microscope obtained in example 1 is shown in FIG. 1. As can be seen from fig. 1, the mesoporous molecular sieve has a typical 1D pore structure. Similarly, examples 2 and3, the mesoporous molecular sieve SBA-15 obtained by the method has a typical 1D pore structure.
TABLE 1
As can be seen from Table 1, when the mesoporous molecular sieve supported catalysts obtained in examples 1 to 3 and comparative examples 1 to 4 were used in the oxidative coupling reaction of methane, examples 1 to 3 had a large methane conversion rate and a selectivity for more than two hydrocarbons, and after 5 hours of reaction, a high methane conversion rate and a high selectivity for more than two hydrocarbons could still be maintained, and the methane conversion rate, ethane selectivity, etc. of comparative examples 1 to 4 were lower than those of examples 1 to 3, indicating that the mesoporous molecular sieve supported catalysts of the present invention had excellent catalytic performance when used in the oxidative coupling reaction of methane.
As can be seen from comparing example 1 with other examples, the preparation of the mesoporous molecular sieve-supported catalyst, which is particularly excellent in catalytic performance, can be performed in the following manner:
adding template agent P123 into a solution (pH value is 4.2-4.5) formed by hydrochloric acid and deionized water, stirring to enable the P123 to be completely dissolved, carrying out ultrasonic treatment at the temperature of 40-42 ℃ for 2-2.2h, adding tetramethoxysilane (the adding rate of the tetramethoxysilane is 0.1-0.12 g/min), stirring for 10-11min at the rotating speed of 850-860 r/min, adding the pore-expanding agent obtained in preparation example 1, stirring the mixture uniformly at the rotating speed of 120-125 r/min, heating the mixture at the temperature of 40-43 ℃ under the vacuum of 100-105 mbar for 3-3.2h, transferring to the air under the room temperature condition for condensation, and roasting at the temperature of 560-562 ℃ for 4-4.1h in a muffle furnace to obtain the mesoporous molecular sieve, wherein the concentration of the hydrochloric acid is 2-2.2mol/L, the consumption of the hydrochloric acid is 25-25.5mL, the consumption of deionized water is 8-8.2g, and the consumption of the tetramethoxysilane is 2-2.2g;
adding lanthanum nitrate hexahydrate, barium nitrate and lithium nitrate into deionized water, mixing and stirring uniformly, adding the mesoporous molecular sieve prepared in preparation example 1 into the uniformly mixed solution, soaking for 6-6.2h at the temperature of 45-46 ℃, then removing water in the system by using a rotary evaporator to obtain a solid product, placing the solid product into a baking oven at the temperature of 110-112 ℃, drying for 2-2.1h, placing into a muffle furnace, setting the temperature to 650-652 ℃ and roasting for 5-5.2h to obtain the catalyst taking the mesoporous molecular sieve as a carrier, wherein the dosage of barium nitrate is 0.012-0.013g, the dosage of lithium nitrate is 0.005-0.0053g, the dosage of deionized water is 100-110g, and the dosage of mesoporous molecular sieve is 1-1.2g relative to 0.23g of lanthanum nitrate hexahydrate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (28)

1. The catalyst taking the mesoporous molecular sieve as a carrier is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is the mesoporous molecular sieve; the active components comprise La, ba and Li;
wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20;
wherein the average pore diameter of the carrier is 5-10nm.
2. The catalyst according to claim 1, wherein the specific surface area of the carrier is 700-1000m 2 /g；
And/or the pore volume of the carrier is 0.5-2.5cm 3 /g；
And/or the average pore diameter of the carrier is 8-10nm;
and/or, the mole ratio of La, ba and Li is 1:0.005-0.007:1.6-16.
3. The catalyst according to claim 1, wherein the specific surface area of the carrier is 750-900m 2 /g；
And/or, the carrierPore volume of 0.6-2cm 3 /g。
4. A catalyst according to any one of claims 1 to 3 wherein the carrier is present in an amount of 64 to 96.89 wt% based on the total weight of the catalyst;
and/or La in an amount of 3 to 15 wt%;
and/or, the content of Ba is 0.01-2 wt%;
and/or Li content of 0.01-15 wt%;
and/or the active component is present in an oxidized form.
5. A catalyst according to any one of claims 1 to 3 wherein the support is present in an amount of 72 to 94.89 wt% based on the total weight of the catalyst;
and/or, the La content is 5 to 12.5 wt%;
and/or, the content of Ba is 0.4-0.4 wt%;
and/or Li content of 0.5-10 wt%.
6. A method of preparing a catalyst supported on a mesoporous molecular sieve, the method comprising:
(1) Under an acidic condition, carrying out contact reaction on a template agent, a pore-expanding agent, water and a silicon source, and then sequentially carrying out solid-liquid separation and roasting to obtain a mesoporous molecular sieve;
(2) Loading active components on a mesoporous molecular sieve, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.004-0.04:1-20.
7. The method of claim 6, wherein the pore-expanding agent is selected from polystyrene and/or mesitylene;
and/or, the polystyrene nanoparticle has an average diameter of less than 200nm;
and/or, the preparation method of the pore-expanding agent comprises the following steps: in the presence of a solvent, mixing styrene and an initiator for polymerization reaction, and then carrying out solid-liquid separation to obtain the polystyrene nano microsphere.
8. The method of claim 6, wherein the pore-expanding agent is polystyrene nanospheres.
9. The method of claim 7 or 8, wherein the initiator is at least one of persulfate, sulfate, and sulfite; and/or, the persulfate is a water-soluble salt;
and/or the initiator, the styrene and the solvent are used in such an amount that the molar ratio of the initiator, the styrene and the solvent is from 1:50 to 100:3000-4000;
and/or the polymerization is carried out under stirring, and the stirring rotation speed is 400-500 rpm;
and/or the temperature of the polymerization reaction is 70-80 ℃, and the time of the polymerization reaction is 18-24 hours;
and/or adding the initiator into the styrene in a mixing mode, wherein the adding rate of the initiator is 0.1-10g/min based on 1g of styrene, and standing the obtained mixed solution for 20-22h after the adding is completed.
10. The method of claim 7 or 8, wherein the initiator is a persulfate.
11. The method according to any one of claims 6 to 8, wherein in step (1), the pH of the acidic condition is controlled to 2 to 5 using an acidic substance; the acidic substance is at least one of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid;
and/or the template agent is a nonionic surfactant;
and/or, the silicon source is sodium silicate and/or tetramethoxysilane;
and/or, the mole ratio of La, ba and Li is 1:0.005-0.007:1.6-16.
12. The method according to any one of claims 6 to 8, wherein in step (1), the acidic substance is hydrochloric acid;
and/or the template has the general formula EO a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a);
and/or, the silicon source is tetramethoxysilane.
13. The method of any one of claims 6-8, wherein in step (1), the templating agent is EO a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers of formula (I), wherein a has a value of 10-100 and b has a value of 40-80.
14. The method of any one of claims 6-8, wherein in step (1), the templating agent is EO 20 PO 70 EO 20 And/or EO 17 PO 55 EO 17 。
15. The method of claim 9 or 10, wherein in step (1), the template, the water and the silicon source in Si are used in amounts such that the molar ratio of the template, the water and the silicon source in Si is 1:30000-65000:40-60;
and/or the use amount of the pore-expanding agent and the template agent is such that the mass ratio of the pore-expanding agent to the template agent is 3-5:1;
and/or the XRD pattern of the mesoporous molecular sieve has characteristic peaks at 100 DEG + -0.3 DEG, 110 DEG + -0.3 DEG and 200 DEG + -0.3 DEG of 2 theta.
16. The method of claim 6, wherein in step (1), the contacting reaction is performed in the following manner: adding a silicon source into the template agent, wherein the adding rate of the silicon source is 0.1-10g/min based on 1g of the template agent;
and/or, the contact reaction is carried out under vacuum condition, and the vacuum degree is 80-100 mbar; the temperature of the contact reaction is 40-50 ℃ and the time is 2-4h;
and/or, in the step (1), the roasting temperature is 500-600 ℃; the roasting time is 0.5-10h.
17. The method of claim 6, wherein in step (1), the contacting reaction is performed in the following manner: adding a silicon source into the template agent, wherein the adding rate of the silicon source is 0.1-5g/min based on 1g of the template agent;
and/or, in the step (1), the roasting time is 3-9h.
18. The method of claim 6, wherein in step (2), the loading is by: impregnating the mesoporous molecular sieve with impregnating solution containing lanthanum precursor, barium precursor and lithium precursor, and then sequentially drying and roasting to obtain a catalyst taking the mesoporous molecular sieve as a carrier;
and/or the impregnating solution is used in an amount of 80 to 120g per gram of carrier.
19. The loading method according to claim 18, wherein the concentration of the lanthanum precursor in the impregnation liquid is 0.01 to 0.5 wt% in terms of lanthanum element, the concentration of the barium precursor in terms of barium element is 0.001 to 0.3 wt% and the concentration of the lithium precursor in terms of lithium element is 0.0001 to 0.1 wt%.
20. The method of claim 18 or 19, wherein in step (2), the lanthanum precursor is a water-soluble lanthanum salt;
and/or, the barium precursor is a water-soluble barium salt;
and/or, the lithium precursor is a water-soluble lithium salt.
21. The method of claim 18 or 19, wherein in step (2), the lanthanum precursor is selected from at least one of lanthanum nitrate, lanthanum chloride, and lanthanum chlorate;
and/or the barium precursor is selected from barium nitrate and/or barium chloride;
and/or the lithium precursor is selected from lithium nitrate and/or lithium acetate.
22. A method according to claim 18 or 19, wherein in step (2) the lanthanum precursor is lanthanum nitrate;
and/or, the lithium precursor is lithium nitrate.
23. The method according to claim 18 or 19, wherein in step (2), the time of the impregnation is 1-6 hours; the temperature is 30-80 ℃;
and/or the drying temperature is 100-110 ℃ and the drying time is 1-3h;
and/or, in the step (2), the roasting temperature is 500-650 ℃; the roasting time is 4-5h.
24. A method according to claim 18 or 19, wherein in step (2) the time of the impregnation is 1-3 hours.
25. A catalyst supported on a mesoporous molecular sieve, wherein the catalyst supported on a mesoporous molecular sieve is prepared by the method of any one of claims 6 to 24.
26. A process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the mesoporous molecular sieve supported catalyst of any one of claims 1-6 and 25 in the presence of oxygen;
or preparing a catalyst supported on a mesoporous molecular sieve according to the method of any one of claims 6 to 24, and then contacting methane with the catalyst supported on the mesoporous molecular sieve in the presence of oxygen.
27. The method of claim 26, wherein the molar ratio of methane to oxygen is from 2 to 8:1, a step of;
and/or, the contact temperature is 500-750 ℃; the contact time is 1-10h; the pressure of the contact is 0.005-0.5MPa, and the space velocity of methane is 10000-100000 mL/(g.h).
28. The method of claim 26, wherein the molar ratio of methane to oxygen is 3-8:1;
and/or the space velocity of the methane is 20000-75000 mL/(g.h).
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Developing catalytic materials for the oxidative coupling of methane through statistical analysis of literature data;Evgenii V. Kondratenko等;Catal. Sci. Technol.,;第5卷;1668-1677 *
La-Ba系氧化物催化剂用于甲烷氧化偶联;远松月,王连驰,王晓梅,于作龙,吴越;催化学报(01);全文 *

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